JP2013539054A - Method for producing structured particles - Google Patents

Abstract

A process for producing structured particles, specifically nanoparticles, laser printer and copier toners, especially chemical toners having specific product properties. This method results in a toner having improved performance. The method specifically relates to the selection and properties of the base materials and the use of these properties to design toner product properties that result in improved performance.
[Selection figure] None

Description

  The present invention relates to a method for producing structured particles. The present invention also relates to toners for laser printers and copiers, particularly chemical toners having specific product properties that result in toners having improved performance compared to existing aftermarket toners. Alternatively, a method for producing a polymerized toner (PT) is provided.

  The present invention is particularly concerned with the properties of the base material and the use of these properties to design toner product properties that result in improved performance, and the selection of the base material.

  Waxes are used to give toner the ability to fuse without the need for silicone oil in a fusion roller. This is called oilless fixing. The chemical toner method allows better control of wax incorporation than mechanical / conventional methods. However, it is still necessary to control the position of the wax within the toner particles. Currently available chemical toners, particularly chemical toners prepared by latex agglomeration, have the problem that it is difficult to control the position of the wax component in the toner particles.

  The principles of Fujifilm Imaging Colorants Ltd. (FFIC) and Xerox latex agglomeration are similar. Although they mention the need for no wax to be present at or near the surface of the toner particles, their process determines the location of the wax component of the particles (or more specifically, any other sub-particle component). It is not shown that it can be controlled. Mitsubishi overcame this problem to some extent by creating a latex around the wax seeds and also forming a second layer of latex free of wax during the agglomeration process. However, this does not exclude the possibility that some wax-containing latex is present at or near the surface of the toner particles. This approach can also cause other problems, such as charge control agent effects and / or suppression of charge effects from the main latex and colorants.

  Even the slight presence of wax at or near the surface can cause print quality problems and storage stability problems. Similar to the position of the wax component, it is also desirable to control the position of other base materials (sub-components). For example, it may be desirable for a charge control agent (CCA) to be present near the surface. In some cases, it may be desirable for the colorant particles to be close to the surface or remote from the surface, depending on their tribo-electric behavior. In some cases. There can be up to six different latexes in the toner composition. It may be desirable for some of these latexes to be near the surface and some to be away from the surface.

  The present invention creates structured particles such that the base material that is a component of the structured particles is positioned at a location within the toner particles that results in the realization of desirable product attributes that result in improved toner performance. , To improve the quality of chemical toners.

Method 1: Method A) by selection and control of particle component size and particle size distribution (by well-established methods known in the art) to produce a stable nanodispersion of subcomponents. These are described in later sections.
B) Design the particle size and particle size distribution of the components.
C) These nanoparticles can be stabilized in the manner known in the art for destabilizing stable dispersions (eg heat, coagulants (usually multivalent metal salts), with the opposite charge) Surfactant, pH, etc.). We use microwaves to provide heat to generate destabilization events (condensation / aggregation). The inventors have chosen microwaves because it allows for precise control of heat, and thus aggregation, and thus final toner particle size distribution. Also, the method by which we apply microwave radiation is more energy efficient and completely safe. As far as we have investigated, we are the first to apply microwave condensation in the field of chemical toners.
D) This method is used for systems where the subcomponents are stabilized by surfactant (s) with similar functionality. We determine the final position of the component relative to the position of the other component by the relationship between the size and size distribution of the other component (s) and the average size and size distribution of the component. I found out. For example, the inventors have found that it is possible to place the wax towards the center of the PT particles by correlating the size of the other components with the particle size of the wax. In a similar manner, the size and size distribution of all components can be selected and designed to correlate so that they can be placed in the correct location when a destabilization event occurs.
E) In addition, the inventors have found that the toner particle density is important rather than the volume density, tap density reported in the prior art definition of particle density, and the particle size, particle size And the relationship to shape has been found to provide an improvement in quality characteristics that are lacking in currently available toners. It is possible to control the particle density of the toner mainly by controlling the properties of the latex component and the size distribution of all components. Volume density and tap density are densities that include voids inside the particles and voids between the particles. The particle density is the density of toner particles including voids inside the particles and not voids between the particles. The inventors have made it possible to adjust the particle density by making it possible to adjust the voids inside the particles.
F) Good control over the raw material particle size and particle size distribution is important to achieve good control over the PT particle size distribution.
G) We believe it is important to control the properties of the raw material because some characteristics of the structured particles can undergo changes similar to changes in the characteristics of the raw material particles when subjected to the same treatment. I found out. For example, if the particle size of the latex changes when heated or the pH is adjusted, PT particles made from the latex can undergo the same changes in the process. For example, it is possible to make a latex that results in a toner that shrinks slightly during the reinforcement and shape control stages. We take advantage of this property not only to improve toner performance, but also for process control at these stages.

Method 2: Continuous Aggregation Although Method 1 can also yield high quality toners, the inventors have further revealed additional methods that provide more flexibility in the design of structured particles.
A) A stable nanodispersion is produced as described in Method 1.
B) Perform continuous flocculation / aggregation to place components in place. For example, the wax is placed in the center of the final toner particle by first condensing the wax and subsequently condensing other components on the “top” of the coagulated wax component. This method allows for a layered particle structure.

Method 3: Combination of Method 1 and Method 2 By combining Method 1 and Method 2, we have realized further control and flexibility in the realization of the desired structured particles.

  The above description relates to the composition and internal structure of the toner particles which are unblended, ie before any flow additives are blended.

  The external structure or surface composition / structure achieved by the blend of flow additives is equally important in determining toner quality. The three main toner properties affected by the flow additive blend are tribocharge, powder flow, and surface coverage.

  Toner particle density plays a major role in the flow behavior of toner particles. Toner particle hardness is another major characteristic of toner particles that affects the flow additive blending process. If the toner particles are too hard, the flow additive has a tendency to “bounce” on the hard surface and therefore does not adhere well to the toner particles. Even if it adheres to some extent due to electrostatic charge, the flow additive will detach from the surface during storage and cause print quality problems (eg, white spots due to loss of flow additive particles stuck on the OPC drum). May cause. If the toner particles are too soft, the flow additive will be embedded and embedded in the toner particles, losing its effectiveness. The use of a combination of small particle size fluid additive and large particle size fluid additive is recommended (by the fluid additive supplier) to address this issue, but in practice it overcomes the embedding problem It is difficult to do.

  The present invention overcomes this problem by designing the hardness of the toner particles so that the flow additive adheres properly without causing excessive embedding. The inventors define the hardness of the toner by a nanoindentation technique. This technique utilizes AFM (Atomic Forced Microscopy) and involves measuring the distance traveled by the AFM probe in the toner particles for a given applied force. The inventors have found that toners with nanoindentation values below 5 nm (nanometers) are too hard and toners with nanoindentation values above 2000 nm are too soft. The inventors have found that toners with nanoindentation values of 5 nm to 2000 nm, in particular 10 nm to 500 nm, exhibit good adhesion of the flow additive. The hardness of the toner is realized in particular by selecting the latex subcomponent.

  Three external properties (triboelectric charge, powder flowability and surface coverage) need to be optimized so that the toner functions well. These three characteristics are interrelated. The triboelectric charge is measured by a standard “blow-off” technique, and the powder flow is measured by the passage of toner particles through a series of fine sieves (as done in the “Hosokawa Powder Tester”). The surface coverage is measured by image analysis of scanning electron micrographs of toner particles.

  Triboelectric charge is a measure of the contribution of the exposed flow additive adhering to the toner particles and the charge from the exposed toner surface. The flow additive contributes to the triboelectric charge value, and the CCA contributes to the charge rate in addition to the triboelectric charge value. Other subcomponents such as latex and colorants also contribute to the triboelectric charge value. Therefore, it is necessary that the toner surface is not completely covered with the flow additive and that a certain percentage of the toner surface is exposed. The flow characteristics are primarily affected by the amount of flow additive, surface coverage, and blending conditions (blender speed and residence time). The inventors have determined that the following combination of three external properties results in good quality toner: -1 □ C / g to -20 □ C / g (for negatively charged toner), +1 □ C / g to +20 □ C / g (for positively charged toner) triboelectric charge, 10% to 80% (preferably 20% to 70%) surface coverage, and 60% to 100% (preferably 70% to 98%) Flow Number (passage rate (%)).

Particle density measurement.
The particle density is defined as the density of particles that include voids within the particles and not voids between the particles. PoreMatter 33 produced by Quantachrome (which uses mercury to fill the voids between the particles) is used to measure the particle density of the toner particles. The true density of the toner particles is also measured using a Micro Ultracometer 1000 (produced by Quantachrome, which uses helium to penetrate into the voids within the particles).

Wax dispersion process 1.
The wax emulsion can be prepared by a phase inversion method. First, a mixture of at least one wax, such as carnauba and / or candelilla, and a surfactant in a weight ratio of about 8 to 1 is first added to the container. The vessel temperature is raised to a temperature above the melting point of the wax mixture (about 92C). A mixture of deionized water and surfactant in a weight ratio of about 25 to 1 is added to the container containing the molten wax mixture for about 1 hour. The amount of water / surfactant mixture added to the container is determined by the desired total solids content (about 20%). While maintaining the temperature constant, stirring is continued for 30 minutes after completion of the addition of the water-surfactant mixture, after which the vessel is cooled to room temperature and the wax emulsion is discharged. Depending on the choice of surfactant, it may be necessary to control the pH of the mixture to a certain value. The typical average particle size of the wax in the emulsion prepared by this method is 800 microns.
Wax 1a had an average size of 120 nm.
Wax 1b had an average size of 405 nm.
Wax 1c had an average size of 628 nm.

Wax dispersion process 2.
At least one wax in a weight ratio of about 20: 5: 75, such as carnauba and / or candelilla, surfactant and deionized water is added to the container. Depending on the choice of surfactant, it is necessary to control the pH of the mixture to a certain value. Activate the agitator in the container. The vessel temperature is raised to a temperature above the melting point of the wax mixture (about 92C). Stirring is maintained for 30 minutes. Circulate the mixture using a high pressure homogenizer for 30 minutes in the recirculation line. The processing pressure of the homogenizer is 150 MPa. The flow rate is selected so that the entire volume in the container rotates about 3 times. Recirculation is stopped and the vessel temperature is cooled to room temperature, after which the wax emulsion is discharged. The typical average particle size of the wax in the emulsion prepared by this method is 400 microns.
Wax 2a had an average size of 125 nm.
Wax 2b had an average size of 371 nm.
Wax 2c had an average size of 650 nm.

  The wax used in the present invention may take the form of natural organic wax, synthetic organic wax and silicone wax. These waxes can include high molecular weight carboxylic acids and esters of higher molecular weight alcohols, paraffin waxes, hydrocarbon waxes, natural plant waxes and synthetic waxes. Examples of natural waxes are beeswax, spermaceti, hydrogenated castor oil wax and hydrogenated oil. Plant waxes include candelilla, carnauba, orange peel wax, Japanese wax, montan wax and bayberry wax.

Dye dispersion process 1
A mixture of yellow pigment, charge agent, surfactant and deionized water in a weight ratio of 19: 7: 3: 71 is prepared. Several biodegradation inhibitors can be added to the mixture. The mixture is treated with a high shear device for 10 minutes to make it homogeneous. In a batch ball mill, 50% volume of each mill grinding chamber is filled with beads having a particle size of about 0.6 microns to 0.8 microns. Each milling chamber is filled with the dye mixture leaving 20% space. Run the mill for 3 hours. Drain the mixture from the milling chamber and separate the mixture from the beads. The average particle size of the dye mixture is measured to be 180 nanometers.

Dye dispersion process 2
A mixture of black pigment, surfactant and deionized water in a weight ratio of 21: 3.5: 75.5 is prepared. Several biodegradation inhibitors can be added to the mixture. The mixture is treated with a high shear device for 5 minutes to make it homogeneous. In a batch ball mill, 50% volume of each mill grinding chamber is filled with beads having a particle size of about 0.6 microns to 0.8 microns. Each milling chamber is filled with the dye mixture leaving 22% space. The mill is run for 2.5 hours. Drain the mixture from the milling chamber and separate the mixture from the beads. The average particle size of the dye mixture is measured to be 120 nanometers.

Dye dispersion process 3
A 500 liter mixture of magenta dye, charge agent, surfactant and deionized water in a weight ratio of 18: 6: 4: 72 is prepared in a vessel equipped with a stirrer and cooling jacket. Several biodegradation inhibitors can be added to the mixture. The mixture is processed for 10 minutes by a high shear device mounted in the container to make it homogeneous. Circulate the mixture using a high pressure homogenizer for 60 minutes in the recirculation line. During that 60 minutes, cooling water is used to maintain the container at room temperature. The processing pressure of the homogenizer is 180 MPa. Drain the mixture from the container. The average particle size of the dye mixture is measured to be 190 nanometers.

Dye dispersion process 4
A 500 liter mixture of cyan dye, surfactant and deionized water in a weight ratio of 23: 4: 73 is prepared in a raw material vessel equipped with a stirrer and a cooling jacket. Several biodegradation inhibitors can be added to the mixture. The mixture is processed for 10 minutes by a high shear device mounted in the container to make it homogeneous. The mixture is transferred to continuous bead slurry mills such as Netzsch's LMZ ZETA mill and Romaco's FlymaKoruma Stirrer Bead CoBall. Send the processed material to the product container. 8C of cold water is used in the raw material container and mill to maintain a processing temperature of less than 20C. Process the mixture 15 times by mill and stop the process. The average particle size of the dye mixture is measured and is 175 nanometers.

Latex Latex was produced by a conventional emulsion polymerization process. The monomers consisted of 5% minor components including styrene (72% -85%), butyl acrylate (10% -22%) and hydroxyl functional monomers and acrylate monomers. Various levels of standard thiols were used as chain transfer agents (CTA) to control the molecular weight of the latex. Ammonium persulfate was used as the initiator and a proprietary ionic surfactant was used as the emulsifier.
Latex 1: average particle size 101 nm, weight average molecular weight (Mw) of 24500, number average molecular weight (Mn) of 7300.
Latex 2: Prepared by the same method as Latex 1 except that the trace component contains acrylic acid and methacrylic acid. Average particle size of 98 nm, Mw 22000, Mn 7500.
Latex 3: produced in the same manner as Latex 2 except that the amount of CTA was reduced. 105 nm average particle size, Mw 120,000, Mn 23000.
Latex 4: Prepared in the same manner as Latex 3 except that the amount of CTA was further reduced. Average particle size of 110 nm, Mw 550000, Mn 70000.

Toner Toner 1: Patented stirrer capable of low shear uniform mixing of 86 parts latex, 6 parts wax, 6 parts colorant and 2 parts CCA and 22 liters of deionized water Were mixed in a 50 liter reactor equipped with The dispersion was mixed at ambient temperature. Subsequently, the dispersion was heated to the cloud point of the surfactant of the system to initiate nucleation (condensation). Optionally, after nucleation (if Tg was higher than the cloud point of the surfactant), the mixture was heated to the glass transition temperature (Tg) of the latex used. The nucleated mixture was held at this temperature for 2 hours to reinforce the formed toner particles. Subsequently, the dispersion was further heated to a temperature above Tg and held at this temperature to effect shape and morphology control. After this step, the mixture was cooled, filtered, washed and dried to obtain a dry toner powder. Subsequently, the toner was blended with a flow additive in a high energy blender to achieve a functional formulated toner. The resulting toner had an average size of 8.2 microns (micrometers) and the ratio of volume average particle size (d50v) to log average particle size (d50n) was 1.45.

  Toner 2: similar to that described in Example 1 except that the surfactant is heated to the cloud point by passing the dispersion mixture through an external flow loop equipped with a microwave device. Prepared. The resulting toner had an average size of 7.9 microns (micrometers) and the ratio of volume average particle size (d50v) to log average particle size (d50n) was 1.19.

  A lower d50v / d50n ratio means a narrower distribution, resulting in a better quality of the toner. This example shows the advantages of performing nucleation by microwaves in the outer flow loop.

Toner 3: A toner similar to Toner 2 was prepared using Latex-L1 and Wax-1a.
Toner 4: A toner similar to Toner 2 was prepared using Latex-L1 and Wax-1b.
Toner 5: A toner similar to Toner 2 was prepared using Latex-L1 and Wax-1c.

  Image analysis of toner 3, toner 4 and toner 5 flakes using a transmission electron microscope (TEM) reveals that the wax area in toner 3 is uniformly distributed throughout the toner and has an average size of 0.5 microns. Was. On the other hand, for toner 5, the wax was concentrated towards the center of the toner particles and had an average size of 2.6 microns. Regarding toner 4, the average wax size was 1.6 microns, and the wax was not distributed more uniformly than toner 3, but was not as concentrated at the center as the wax in toner 5. These toners were also tested in a commercial printer. The results are shown in the following table.

末尾の「０」の数字はトナーの製造直後の試験の結果を意味しており、末尾の「４」の数字は４ヶ月の保管の後に実施した試験の結果を意味している。

The number “0” at the end means the result of the test immediately after the production of the toner, and the number “4” at the end means the result of the test carried out after storage for 4 months.

  An optical density greater than 1.2 is considered acceptable, a background less than 0.005 is considered acceptable, a transfer efficiency higher than 75% is considered acceptable, and a uniform print quality is considered acceptable.

  The results show that a toner (toner 3) with a similar initial wax size to latex size ratio is unacceptable. After 4 months storage, toner 4 is also unacceptable. Only toner 5 with the highest ratio of latex size to wax size shows acceptable and consistent results, with large size wax concentrated in the center of the toner particles.

  Toner 6: A toner similar to the toner 2 was prepared except that the average sizes of latex, colorant, CCA and wax were arbitrarily selected from the patent literature.

  Toner 7: To achieve the desired particle structure design, a toner similar to toner 6 was prepared except that the average sizes of latex, colorant, CCA and wax were in specific interrelated ratios.

  Toner 7 showed better printing performance than Toner 6.

Toner 8: Prepared in the same manner as Toner 2 except that Latex 2 was used. The particle density of toner 2 was 990 kg / m ³ but toner 8 was 1070 kg / m ³ . Since the voids between the particles formed by nucleation and strengthening of acrylic acid and methacrylic acid were reduced, higher particle densities could be realized.

  Toner 8 provided greater flexibility in the implementation of the surface additive formulation and achieved the desired flow and charge characteristics.

Toner 9: prepared in the same manner as toner 8, except that small amounts of latex 3 and latex 4 (10 parts and 5 parts, respectively) were added. The particle density was 1095 kg / m ³ . The obtained nanoindentation value was 25 nm. For toner 8, the nanoindentation value was 200 nm.

  Toner 8 and toner 9 were blended in the same manner. Viewing the SEM image shows that more fluid additive is visible in toner 9 than toner 8 and this indicates that more fluid additive is embedded in toner 8 than toner 9. It was.

  Toner 9 had a flow rate of 94%, a tribo of -9 microcoulombs per gram, and a surface coverage of 75%.

  Toner 8 had a flow rate of 83%, a tribo of -5 microcoulombs per gram, and a surface coverage of 55%.

  Also from the printing result, it was confirmed that the toner 9 is superior to the toner 8.

  Toner 10: 6 parts wax and 2 parts CCA and 22 liters of deionized water were mixed in a 50 liter reactor equipped with a patented stirrer capable of low shear uniform mixing. . The dispersion was mixed at ambient temperature. Subsequently, the dispersion was heated to the cloud point of the surfactant of the system to initiate nucleation (condensation). The nucleated mixture was held at this temperature for 1 hour to reinforce the formed initial particles. The mixture was cooled to 25C. 86 parts latex and 6 parts colorant were added to the reactor. The dispersion was mixed at ambient temperature. Subsequently, the dispersion was heated to the cloud point of the surfactant of the system to initiate further nucleation (condensation). Subsequently, the dispersion was further heated to a temperature above Tg and held at this temperature to effect shape and morphology control. After this step, the mixture was cooled, filtered, washed and dried to obtain a dry toner powder. Subsequently, the toner was blended with a flow additive in a high energy blender to achieve a functional formulated toner. The resulting toner had an average size of 8.7 microns (micrometers) and the ratio of volume average particle size (d50v) to log average particle size (d50n) was 1.22.

  Toner 11: Both in a 50 liter reactor equipped with a patented stirrer capable of low shear uniform mixing of 6 parts wax and 2 parts colorant and 22 liters of deionized water together Mixed. The dispersion was mixed at ambient temperature. Subsequently, the dispersion was heated to the cloud point of the surfactant of the system to initiate nucleation (condensation). The nucleated mixture was held at this temperature for 1 hour to reinforce the formed initial particles. The mixture was cooled to 25C. 86 parts of latex, 2 parts of CCA and 4 parts of colorant were added to the reactor. The dispersion was mixed at ambient temperature. Subsequently, the dispersion was heated to the cloud point of the surfactant of the system to initiate further nucleation (condensation). Subsequently, the dispersion was further heated to a temperature above Tg and held at this temperature to effect shape and morphology control. After this step, the mixture was cooled, filtered, washed and dried to obtain a dry toner powder. Subsequently, the toner was blended with a flow additive in a high energy blender to achieve a functional formulated toner. The resulting toner had an average size of 8.6 microns (micrometers) and the ratio of volume average particle size (d50v) to log average particle size (d50n) was 1.23.

  Toner 10 and toner 11 were also tested in a commercial printer. The results are shown in the following table.

  The results show that the position of the wax, CCA, dye and latex components play a major role in the final print quality, even when using the same composition and final toner physical properties. The toner 10 has wax and CCA in the center of the toner particles. The toner 11 has a wax and a certain amount of colorant in the center thereof, and the outer layer is uniformly formed of latex, CCA and colorant. The print quality of the ideally structured toner 11 is very good.

  While the invention has been described in connection with certain preferred embodiments, those skilled in the art will recognize that various changes and modifications can be made without departing from the scope of the invention as defined in the following claims. It will be obvious.

Claims (24)

A method in which the base material produces at least two structured particles,
a. Preparing a stable dispersion of a predetermined size of at least one of each base material;
b. Mixing together the dispersion of step "a", wherein the particle size distribution between the base material particles is in a predetermined ratio; and
c. Nucleating (aggregating) the mixture of step “b”;
d. Obtaining structured particles; and
Including a method.   The method for producing structured particles according to claim 1, wherein the structured particles are cosmetics / pharmaceuticals / pigments.   Structured particles prepared by the method of claim 1 or 2. A method for producing a toner comprising at least two basic materials: latex and colorant comprising:
a. Preparing a stable dispersion of at least one of each base material, wherein said base material has an average particle size of less than 1000 nm, preferably less than 500 nm;
b. Mixing together the dispersion of step "a", wherein the particle size distribution between the base material particles is in a predetermined ratio; and
c. Heating the mixture of step “b” to a temperature up to the Tg of the latex base material for nucleation (condensation);
d. Optionally, heating the mixture to a temperature above the Tg of the latex, strengthening the particles and controlling the shape of the particles;
e. Obtaining toner particles;
A method for producing a toner, comprising:   5. The method of claim 4, wherein there are at least four base materials: latex, colorant, wax and charge control agent.   5. The method of claim 4, wherein the heating step is performed by use of microwave radiation to control particle nucleation (aggregation).   Said stable dispersion of the base material latex is prepared by emulsion polymerization in order to obtain a dispersion having a determined molecular weight, molecular weight distribution, glass transition temperature, melting point and characterized by an accurate particle size and particle size distribution. The method according to claim 4.   The method of claim 4, wherein the base material latex has an average particle size of 50 nm to 500 nm and a particle size distribution (d90 / d10) of 1.5-10. Particularly preferably, the average particle size range is from 50 nm to 150 nm and the particle size distribution is from 1.5 to 4.   5. A method according to claim 4, wherein the base material latex is of more than one, preferably up to 6 different types.   The method of claim 4, wherein the stable dispersion of base material colorant is prepared by media milling or use of a high pressure homogenizer.   The method of claim 4, wherein the base material colorant has a particle size of 50 nm to 1000 nm and a particle size distribution (d90 / d10) of 1.5 to 12. Particularly preferably, the average particle size range is from 50 nm to 350 nm and the particle size distribution is from 1.5 to 4.   The stable dispersion of a base material wax is prepared by emulsification of a melted wax with an aqueous mixture or by melting the wax in the presence of an emulsifier in an aqueous environment and passing through a high pressure homogenizer. 4. The method according to 4.   The method according to claim 4, wherein the base material wax has a particle size of 100 nm to 2000 nm and a particle size distribution (d90 / d10) of 1.5 to 15. Particularly preferably, the average particle size range is from 100 nm to 1000 nm and the particle size distribution is from 2 to 10.   5. A method according to claim 4, wherein the base material wax is of more than one, preferably at most 5 different types.   5. The method of claim 4, wherein the stable dispersion of base material charge control agent is prepared by use of a high pressure homogenizer.   5. The method of claim 4, wherein the base material charge control agent has a particle size of 50 nm to 1000 nm and a particle size distribution (d90 / d10) of 1.5 to 15. Particularly preferably, the average particle size range is from 50 nm to 350 nm and the particle size distribution is from 1.5 to 4.   5. A method according to claim 4, wherein the base material charge control agent is of more than one, preferably at most 5 different types.   5. The method of claim 4, wherein at the predetermined ratio of particle size distribution between the base material particles, the ratio of latex to colorant, wax and CCA particle size is 0.1 to 1. The particle size ratios of colorant to latex, wax and CCA are 10: 1, 0.2: 1, 0.2: 1 respectively. The particle size ratios of wax to latex, colorant and CCA are 10: 1, 5: 1 and 10: 1 respectively. The CCA to latex and colorant and wax particle size ratios are 10: 1, 5: 1 and 0.1: 1, respectively.   19. A method according to any one of claims 4 to 18, wherein the toner particles obtained in step "e" of claim 1 have an average size of 5 microns to 10 microns, preferably 6 microns to 9 microns. The following optional steps can be added:
a. Filtering and washing the toner particles;
b. Drying the toner particles;
c. Blending flow additives and / or altering surface morphology and / or charge control and screening;
The method of claim 4, further comprising: A process for producing toner from at least two basic materials: latex, wax, colorant and charge control agent,
a. Preparing a stable dispersion of at least one of each base material, wherein said base material has an average particle size of less than 1000 nm, preferably less than 500 nm;
b. Continuously condensing the dispersion of step "a" by heating, wherein the particle size distribution between the base material particles is in a predetermined ratio; and
c. Optionally heating the mixture to a temperature above the Tg of the latex to strengthen the particles and control the shape of the particles, comprising the steps of:
d. Obtaining toner particles;
A method for producing a toner, comprising:   A polymerized toner prepared by the method according to claim 1. A polymerized toner comprising at least one of each of four basic materials: latex, wax, colorant and charge control agent,
a. ^{700kg / m 3 ~1500kg / m 3} , preferably particle density of ^{800kg / m 3 ~1200kg / m 3} ,
b. An average nanoindentation value of 5 nm to 2000 nm,
c. Particle aspect ratio of 1.0 to 5.0.
d. Positive or negative 0.5 μC / g to 20 μC / g monocomponent charge value, surface coverage by surface additive of 10% to 100% of toner surface area, and flow rate of 40% to 100%,
A polymerized toner having: a. A particle density of 1000 to 1200, in particular 1025 to 1125,
b. An average nanoindentation value of 20 nm to 1000 nm, in particular 20 nm to 250 nm,
c. A particle aspect ratio of 1.0 to 2.5, in particular 1.0 to 1.5,
d. Surface coverage of 20% to 90%, in particular 40% to 80%,
e. 60% to 100%, especially 82% to 98% flow number,
The polymerized toner according to claim 23, comprising: